Synthesis of End-Functionalized Polymers by Means of Living Anionic Polymerization. 9. Synthesis of Well-Defined End-Functionalized Polymers with One, Two, Three, or Four Monosaccharide Residues

Abstract

Well-defined end-functionalized polystyrenes and polyisoprenes with monosaccharide residues were synthesized by the termination reactions of the anionic living polymer of styrene or isoprene with benzyl chloride derivatives containing acetal-protected glucofuranose (1), fructopyranose (2), galactopyranose (3), and sorbofuranose (4). Furthermore, novel well-defined end-functionalized polymers with two, three, and four monosaccharide residues were successfully synthesized by reacting polystyryllithium with 1,1-bis{3‘-[(1,2;5,6-di-O-isopropylidene-α-d-glucofuranose-O-3-yl)methyl]phenyl}ethylene (5), followed by treating with methanol, 1 (or 3), and the octyliodide containing two acetal-protected glucofuranoses (6), respectively. The end-functionalized polystyrenes with one and two glucose residues thus synthesized were found by static light scattering measurements to form reverse micelles in cyclohexane by aggregating several polymer chains.

Recent developments in anionic polymerization

“…At a time when the recently discovered controlled radical polymerization [2*] is viewed as a much less demanding process, anionic polymerization still remains an important method, well-suited to kinetic studies [3*], the synthesis of polymers of predictable molecular weight (MW) with a narrow molecular weight distribution (MWD), tailoring of block copolymers [4,5*,6-9], design of nonlinear molecular architectures [10**, 11] and telechelic polymers [12][13][14][15][16][17], and stereoregular polymerization [18,19]. Major progress in mechanistic studies and macromolecular engineering reported in the past year(s) is to be found in the very challenging field of the anionic polymerization of (meth)acrylic monomers.…”

Synthesis of Glycoconjugated Branched Macromolecular Architectures

“…By anionic polymerizations, Hirao and co-workers 75 reported that monosaccharides were introduced into the chain-ends of polystyrene (PSt) using benzyl chloride derivatives containing acetal-protected monosaccharides as terminating agents. Furthermore, they reported that the end-functionalized PSt's with a 2, 4, 6, 8, and 12 monosaccharide residues were successfully prepared by an ''iterative'' approach using 1,1-diphenylethylene derivatives with 2 or 4 monosaccharide residues.…”

“…Furthermore, they reported that the end-functionalized PSt's with a 2, 4, 6, 8, and 12 monosaccharide residues were successfully prepared by an ''iterative'' approach using 1,1-diphenylethylene derivatives with 2 or 4 monosaccharide residues. 75,76 The resulting polymers showed an aggregation property to generate a reversed polymer micelle, in which the aggregation number depended on the number of the introduced monosaccharide …”

Recent advance in syntheses and applications of well-defined end-functionalized polymers by means of anionic living polymerization

“…3. In fact, a number of hydroxy groups from 2 to 4 were introduced at polystyrene chain ends by reacting with 5-7 [17,18].…”

“…It involves living end-functionalization reaction using DPE derivatives coupled with use of functionalized terminators. Like the functionalization reactions with DPE derivatives reported previously, the polystyrene end-functionalized with two glucose residues was obtained by reacting polystyryllithium with the DPE derivative 36 with two acetal protected-glucofuranose moieties [55].…”